EP3405167A1 - Process for the maintaining of a ratio of isomers of carotenoids - Google Patents

Process for the maintaining of a ratio of isomers of carotenoids

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Publication number
EP3405167A1
EP3405167A1 EP17700460.3A EP17700460A EP3405167A1 EP 3405167 A1 EP3405167 A1 EP 3405167A1 EP 17700460 A EP17700460 A EP 17700460A EP 3405167 A1 EP3405167 A1 EP 3405167A1
Authority
EP
European Patent Office
Prior art keywords
alkali hydroxide
compound
formula
koh
formulation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17700460.3A
Other languages
German (de)
French (fr)
Inventor
Franziska KREISSIG
Christian SCHÄFER
Joachim Ulrich
Elodie VERDURAND
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
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Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Publication of EP3405167A1 publication Critical patent/EP3405167A1/en
Withdrawn legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/179—Colouring agents, e.g. pigmenting or dyeing agents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/105—Plant extracts, their artificial duplicates or their derivatives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40—Colouring or decolouring of foods
    • A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
    • A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
    • A23L5/44—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/592—Mixtures of compounds complementing their respective functions
    • A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a process for the maintaining of a ratio of stereoisomers of carotenoid compounds, to specific formulations and to the use of such specific formulations.
  • Carotenoids (which are also named carotenoid compounds in the context of the pre- sent patent application) generally consist of conjoined units of the hydrocarbon iso- prene, with alternating single and double bonds. The carotenoids absorb light energy of certain frequencies and transfer it to chlorophyll for use in photosynthesis.
  • Carotenoids are nutritionally important for animals as well as human beings, and also have antioxidant properties.
  • the carotenoids are classified into two groups:
  • the carotenoids when found in nature, are mainly existing in the all-trans stereoisomer ⁇ form. But the carotenoids have a tendency to steroisomerise (that means to transform into other stereoisomeric forms).
  • E- forms, Z-forms and mixtures of E/Z-forms are meant by stereoisomeric forms. Stere- oisomerisation usually results in a mixture of many different stereoisomeric structures: such as: All E-Form
  • carotenoid compounds All stereoisomeric forms of the carotenoid compounds usually have different properties in regard to i.e. light absorption, bioavailability etc. So when the isomerisation takes place the properties of a formulation comprising carotenoid compounds can change.
  • the goal of the present invention was to find a process, which maintains a ratio of stereoisomers of carotenoid compounds, so that the properties of a formulation comprising carotenoids are not changing.
  • the isomerisation of carotenoid compounds is influ- enced by the addition of at least one alkali hydroxide and/or earth alkali hydroxide.
  • This addition results that the stereoisomeric form (or also a mixture of two or more stereoisomeric forms) are stabilised.
  • the alkali and/or earth alkali hydroxide has the following formula M n+( OH) n , wherein M signifies the alkali or earth alkali metal.
  • M signifies the alkali or earth alkali metal.
  • alkali hydroxides (formula MOH. more preferably NaOH or KOH, most preferred is KOH.
  • the carotenoid compounds are present in the form of a solution or emulsion.
  • the solution or emulsion can then in a further step be dried (spray dried, freeze dried), mixed with other formulations or ingredients, etc.
  • the concentration of the carotenoid compound in such a formulation can vary de- pending on the use of such a formulation.
  • Suitable solvents are such wherein carotenoid compounds are soluble, such as ethylacetate, methylenechloride, chloroform, acetone, etc.
  • an emulsion system is usually an oil-in-water emulsion.
  • any commonly known and used oils and emulsifiers are used.
  • the choice of the oil as well as the emulsifier depends on the use of the formulation. In case a food or feed product is produced, then these compounds need to be food or feed grade.
  • Suitable oils can be from any origin. They can be natural, modified or synthetic. If the oils are natural, they can be plant or animal oils. Suitable oils are i.e.
  • coconut oil corn oil, cottonseed oil, olive oil, palm oil, peanut oil, canola oil, safflower oil, sesame oil, soybean oil, sunflower oil, hazelnut oil, almond oil, cashew oil, macadamia oil, mon- gongo nut oil, pracaxi oil, pecan oil, pine nut oil, pistachio oil, sacha Inchi (Plukenetia volubilis) oil, walnut oil, polyunsaturated fatty acids (such as triglyceride and/or ethyl ester, (for example arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid and ⁇ -linolenic acid and/or ethyl ester).
  • polyunsaturated fatty acids such as triglyceride and/or ethyl ester, (for example arachidonic acid, eicosapentaenoic acid, docosa
  • emulsifier Any commonly known and used emulsifier can be used.
  • the emulsifier can be cho- sen depending on the final use of the formulation afterwards.
  • Suitable emulsifiers are i.e. modified (food) starches, pectin, alginate, carrageenan, furcellaran, chitosan, maltodextrin, dextrin derivatives, celluloses and cellulose derivatives (e.g.
  • cellulose acetate methyl cellulose, hydroxypropyl methyl cellulose
  • lignosulfonate polysaccharide gums (such as gum acacia, gum arabic, flaxseed gum, ghatti gum, tamarind gum and arabinogalactan), gelatine (bovine, fish, pork, poultry), plant proteins (such as concentrates, isolates, hydrolysates, etc.
  • the starches can be modified physically and chemically.
  • Pregelatinized starches are examples of physically modified starches.
  • Acidic modified, oxidized, OSA-modified, cross-linked, starch esters, starch ethers and cationic starches are examples of chemically modified starches.
  • the formulations can comprise further auxiliary agents.
  • the auxiliary agent(s) can vary.
  • These auxiliary agents can be useful for the formulation by further improving its properties, such as physical stability, storage stability, visual perception, etc.
  • Auxiliaries can also be useful for the application in the food, feed or personal care product by improving the property of these compositions, physical stability, storage stability, visual perception, controlled release in the Gl-tract, pH control, oxidation resistant, etc.
  • the concentration of these auxilia- ries can vary, depending on the use of these auxiliaries.
  • Preferred carotenoid compounds are the following ones:
  • At least one alkali hydroxide and/or earth alkali hydroxide is added in an amount of 0.0001 wt-% to 1 wt-%, based on the total weight of the carotenoid compound or mixture thereof.
  • the amount of the at least one alkali hydroxide and/or earth alkali hydroxide is the solved amount thereof in the solvent.
  • the process is usually carried out at a temperature from 15 °C to 160 °C, preferably 20 °C to 130 °C, more preferably 20 °C to 1 10 °C.
  • the process is usually carried out at a pressure of 1 bar to 10 bar, preferably 1 bar to 8 bar, more preferably 1 bar to 5 bar.
  • the carotenoid compounds comprising at least one alkali and/or earth al- kali hydroxide in an amount of 0.0001 wt-% to 1 wt-%, can be used as such or be used to be further formulated.
  • the ratio of the isomers is stabilised in the composition as such (only carotenoid compound and alkali hydroxide and/or earth alkali hydroxide as well in formulations com- prising such a composition.
  • a preferred embodiment of the present invention relates to a process for maintaining a ratio of stereoisomers of compound of formula (la)
  • a preferred embodiment of the present invention relates to a process for maintaining a ratio of stereoisomers of compound of formula (le)
  • the alkali and/or earth alkali hydroxide can be added as a solid form as well as a solution (or a combination of both). Furthermore the present invention also relates to a formulation comprising at least one carotenoid compound of formula (I) wherein Ri and R2 are independently of each other
  • the carotenoid compounds comprising at least one alkali hydroxide and/or earth alkali hydroxide in an amount of 0.0001 wt-% to 1 wt-%, can be used as such or used to be further formulated.
  • the fornnulation as described above can be used in food, feed or personal care products.
  • the amount of a formulation as described above used in food, feed or personal care products depends on the food, feed or personal care products
  • Fig. 1 HPLC data, additive-free, pure chloroform, at 40 °C (example 1 )
  • Fig. 2 HPLC data, pure chloroform in presence of KOH, at 40 °C. (example 2)
  • Fig. 3 HPLC data in additive-free, water-saturated methylene chloride, at 30 °C. (example 3)
  • Fig. 4 HPLC data in water-saturated methylene chloride in presence of KOH, at 30 °C. (example 4)
  • Fig. 5 UVA/IS data in additive-free, water-saturated chloroform, at 40 °C. (example 5)
  • Fig. 6 UVA/IS data in water-saturated chloroform in presence of KOH, at 40 °C. (example 6)

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Abstract

The present invention relates to process for the maintaining of a ratio stereoisomers of carotenoid compounds by using of at least one alkali hydroxide and/or earth alkali hydroxide, to specific formulations and to the use of such specific formulations.

Description

PROCESS FOR THE MAINTAINING OF A RATIO OF ISOMERS OF CAROTENOIDS
The present invention relates to a process for the maintaining of a ratio of stereoisomers of carotenoid compounds, to specific formulations and to the use of such specific formulations.
Carotenoids (which are also named carotenoid compounds in the context of the pre- sent patent application) generally consist of conjoined units of the hydrocarbon iso- prene, with alternating single and double bonds. The carotenoids absorb light energy of certain frequencies and transfer it to chlorophyll for use in photosynthesis.
Carotenoids are nutritionally important for animals as well as human beings, and also have antioxidant properties.
The carotenoids are classified into two groups:
• carotenes (do only contain H and C atoms), and
• xanthophylls (do also contain O-atoms).
The carotenoids, when found in nature, are mainly existing in the all-trans stereoisomer^ form. But the carotenoids have a tendency to steroisomerise (that means to transform into other stereoisomeric forms). In the context of the present invention E- forms, Z-forms and mixtures of E/Z-forms are meant by stereoisomeric forms. Stere- oisomerisation usually results in a mixture of many different stereoisomeric structures: such as: All E-Form
The "*"'s (=asterisks) are the positions of the endgroups (Ri and R2)
All stereoisomeric forms of the carotenoid compounds usually have different properties in regard to i.e. light absorption, bioavailability etc. So when the isomerisation takes place the properties of a formulation comprising carotenoid compounds can change.
Therefore the goal of the present invention was to find a process, which maintains a ratio of stereoisomers of carotenoid compounds, so that the properties of a formulation comprising carotenoids are not changing.
From the prior art (WO2013010820) it is known that specific mineral salts are able to stabilize a ratio of stereoisomers of carotenoid compounds.
Due to the importance of such a process, there is a constant need for improvements and alternatives.
Surprisingly, it was found that the isomerisation of carotenoid compounds is influ- enced by the addition of at least one alkali hydroxide and/or earth alkali hydroxide. This addition results that the stereoisomeric form (or also a mixture of two or more stereoisomeric forms) are stabilised. The stereoisomerisation is prevented or slowed down. Therefore, the present invention relates to a process for the maintaining of a ratio of stereoisomers of carotenoid compounds of formula (I) wherein Ri and R2 are independently of each other
characterised in that at least one compound of formula (I)
is mixed with 0.0001 wt-% to 1 weight-% (wt-%), based on the total weight of the compound(s) of formula (I), of at least one alkali hydroxide and/or earth alkali hydroxide (dissolved in the solvent). The amount of the at least one alkali hydroxide and/or earth alkali hydroxide is the amount which is dissolved in the solvent. Usually a higher amount of the at least one alkali hydroxide and/or earth alkali hydroxide is added, to ensure that the solution is saturated. The alkali and/or earth alkali hydroxide has the following formula Mn+(OH)n, wherein M signifies the alkali or earth alkali metal. Preferred are alkali hydroxides (formula MOH. more preferably NaOH or KOH, most preferred is KOH.
The asterisks mark the bond to the backbone. Usually the carotenoid compounds are present in the form of a solution or emulsion. The solution or emulsion can then in a further step be dried (spray dried, freeze dried), mixed with other formulations or ingredients, etc.
The concentration of the carotenoid compound in such a formulation can vary de- pending on the use of such a formulation. Suitable solvents are such wherein carotenoid compounds are soluble, such as ethylacetate, methylenechloride, chloroform, acetone, etc.
If an emulsion system is used, then it is usually an oil-in-water emulsion. For such an emulsion any commonly known and used oils and emulsifiers are used. The choice of the oil as well as the emulsifier depends on the use of the formulation. In case a food or feed product is produced, then these compounds need to be food or feed grade. Suitable oils can be from any origin. They can be natural, modified or synthetic. If the oils are natural, they can be plant or animal oils. Suitable oils are i.e. coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, canola oil, safflower oil, sesame oil, soybean oil, sunflower oil, hazelnut oil, almond oil, cashew oil, macadamia oil, mon- gongo nut oil, pracaxi oil, pecan oil, pine nut oil, pistachio oil, sacha Inchi (Plukenetia volubilis) oil, walnut oil, polyunsaturated fatty acids (such as triglyceride and/or ethyl ester, (for example arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid and γ-linolenic acid and/or ethyl ester).
Any commonly known and used emulsifier can be used. The emulsifier can be cho- sen depending on the final use of the formulation afterwards. Suitable emulsifiers are i.e. modified (food) starches, pectin, alginate, carrageenan, furcellaran, chitosan, maltodextrin, dextrin derivatives, celluloses and cellulose derivatives (e.g. cellulose acetate, methyl cellulose, hydroxypropyl methyl cellulose), lignosulfonate, polysaccharide gums (such as gum acacia, gum arabic, flaxseed gum, ghatti gum, tamarind gum and arabinogalactan), gelatine (bovine, fish, pork, poultry), plant proteins (such as concentrates, isolates, hydrolysates, etc. from peas, soybeans, castor beans, cot- tonseed, potatoes, sweet potatoes, manioc, canola, sunflowers, sesame, linseed, saf- flower, lentils, nuts, wheat, rice, maize, barley, rye, oats, lupin and sorghum), animal proteins including milk or whey proteins, lecithin, polyglycerol ester of fatty acids, monoglycerides of fatty acids, diglycerides of fatty acids, sorbitan ester, PG ester and sugar ester (as well as derivatives thereof).
The starches can be modified physically and chemically. Pregelatinized starches are examples of physically modified starches. Acidic modified, oxidized, OSA-modified, cross-linked, starch esters, starch ethers and cationic starches are examples of chemically modified starches.
The formulations can comprise further auxiliary agents. Depending for which use the formulations are used, the auxiliary agent(s) can vary. These auxiliary agents can be useful for the formulation by further improving its properties, such as physical stability, storage stability, visual perception, etc. Auxiliaries can also be useful for the application in the food, feed or personal care product by improving the property of these compositions, physical stability, storage stability, visual perception, controlled release in the Gl-tract, pH control, oxidation resistant, etc. The concentration of these auxilia- ries can vary, depending on the use of these auxiliaries.
Preferred carotenoid compounds are the following ones:
Compound of formula (la):
β-carotene
Compound of formula (lb)
α-carotene
Connpound of formula (Ic):
δ-carotene
Compound of formula (le)
Compound of formula (If):
Compound of formula (Ig)
lutein
Compound of formula (li):
zeaxanthin Compound of formula (Ij):
Lycopene
To stabilise a ratio of the carotenoid compounds at least one alkali hydroxide and/or earth alkali hydroxide is added in an amount of 0.0001 wt-% to 1 wt-%, based on the total weight of the carotenoid compound or mixture thereof. Preferably 0.0001 wt-% to 0.9 wt-%, more preferably 0.0001 wt-% to 0.8 wt-%.
As stated above the amount of the at least one alkali hydroxide and/or earth alkali hydroxide is the solved amount thereof in the solvent.
The process is usually carried out at a temperature from 15 °C to 160 °C, preferably 20 °C to 130 °C, more preferably 20 °C to 1 10 °C.
The process is usually carried out at a pressure of 1 bar to 10 bar, preferably 1 bar to 8 bar, more preferably 1 bar to 5 bar.
Afterwards the carotenoid compounds comprising at least one alkali and/or earth al- kali hydroxide in an amount of 0.0001 wt-% to 1 wt-%, can be used as such or be used to be further formulated.
The ratio of the isomers is stabilised in the composition as such (only carotenoid compound and alkali hydroxide and/or earth alkali hydroxide as well in formulations com- prising such a composition.
In case of β-carotene (compound (la)), the stereoisomerisation leads to a shift of the shade of the colour. The All Z-form is more reddish whereas the Z forms are slightly yellowish. Therefore a preferred embodiment of the present invention relates to a process for maintaining a ratio of stereoisomers of compound of formula (la)
characterised in that 0.0001 wt-% to 1 wt-%, based on the total weight of the compound of formula (la), of KOH is added.
In case of astaxanthin (compound (le)), the stereoisomerisation leads to different bi- oavailability of the compound. The all (E) form of astaxanthin has the best bioavailability. Therefore this form (or a form with a high amount of all (E) at least 85 % of all (E)) should be stabilised.
Therefore a preferred embodiment of the present invention relates to a process for maintaining a ratio of stereoisomers of compound of formula (le)
characterised in that 0.0001 wt-% to 1 wt-%, based on the total weight of the compound of formula (le), of KOH is added.
The alkali and/or earth alkali hydroxide can be added as a solid form as well as a solution (or a combination of both). Furthermore the present invention also relates to a formulation comprising at least one carotenoid compound of formula (I) wherein Ri and R2 are independently of each other
and 0.0001 to 1 wt-%, based on the total weight of the compound(s) of formula (I), of at least one alkali hydroxide and/or earth alkali hydroxide.
All preferences for the process also apply for the formulations.
As said above the formulations the carotenoid compounds comprising at least one alkali hydroxide and/or earth alkali hydroxide in an amount of 0.0001 wt-% to 1 wt-%, can be used as such or used to be further formulated. The fornnulation as described above can be used in food, feed or personal care products.
The amount of a formulation as described above used in food, feed or personal care products depends on the food, feed or personal care products
Figures:
Fig. 1 : HPLC data, additive-free, pure chloroform, at 40 °C (example 1 )
Fig. 2: HPLC data, pure chloroform in presence of KOH, at 40 °C. (example 2)
Fig. 3: HPLC data in additive-free, water-saturated methylene chloride, at 30 °C. (example 3)
Fig. 4: HPLC data in water-saturated methylene chloride in presence of KOH, at 30 °C. (example 4)
Fig. 5: UVA/IS data in additive-free, water-saturated chloroform, at 40 °C. (example 5)
Fig. 6: UVA/IS data in water-saturated chloroform in presence of KOH, at 40 °C. (example 6)
The following examples serve to illustrate the invention. All percentages are given in relation to weight and the temperature is given in degree Celsius.
Example 1 (comparison)
49.78 mg astaxanthin were dissolved in 250 mL chloroform. The solution was constantly stirred at 300 rpm and the formulation was tempered at 40 °C. The solution was stored and samples were taken periodically and the concentration of astaxanthin was measured spectrophotometrically at 478 nm.
The result can be seen in Figure 1 .
Example 2
52.84 mg astaxanthin was dissolved in 250 mL chloroform 0.21 g KOH were added (to provide a saturated KOH/CH3CI solution. This means that only a minor amount of the KOH dissolves. This is the case for all examples), and afterwards the solution was constantly stirred at 300 rpm and the formulation was tempered at 40 °C. The solution was stored and samples were taken periodically and the concentration of astaxanthin was measured spectrophotometrically at 478 nm.
The result can be seen in Figure 2. The effect of the KOH (when compared with Example 1 ) can be seen clearly!
Example 3 (comparison)
10.32 mg astaxanthin were dissolved in 50 mL chloroform. The solution was constantly stirred at 300 rpm and was tempered at 40 °C. The solution was stored and samples were taken periodically and the concentration of astaxanthin was measured spectrophotometrically at 478 nm.
The result can be seen in Figure 3.
Example 4
9.14 mg astaxanthin were dissolved in each 50 mL chloroform. 7.76 mg KOH was added to the solution. The solution was constantly stirred at 300 rpm and was tempered at 40 °C. The solution was stored and samples were taken periodically and the concentration of astaxanthin was measured spectrophotometrically at 478 nm. The result can be seen in Figure 4. The effect of the KOH (when compared with Example 3) can be seen clearly!
Example 5 (comparison)
51 .83 mg astaxanthin was dissolved in 250 ml_ chloroform. The solution was constantly stirred at 300 rpm and was tempered at 40 °C. The solution was stored and samples were taken periodically from each of the five beakers and the concentration of astaxanthin was measured spectrophotometrically at 478 nm.
The result can be seen in Figure 5.
Example 6
10.2 mg astaxanthin were dissolved in 50 ml_ chloroform. 96.00 mg KOH were added and afterwards the solution was constantly stirred at 300 rpm and was tempered at 40 °C. The solution was stored and samples were taken periodically and the concentration of astaxanthin was measured spectrophotometrically at 478 nm.
The result can be seen in Figure 6. The effect of the KOH (when compared with Example 1 ) can be seen clearly!

Claims

Claims
1 . A process for the maintaining of a ratio of stereoisomers of carotenoid compounds of formula (I)
characterised in that the compounds of formula (I)
are mixed with 0.0001 wt-% to 1 wt- %, based on the total weight of the compound(s) of formula (I), of at least one alkali hydroxide and/or earth alkali hydroxide.
2. Process according to claim 1 wherein the carotenoid compounds are chosen from the group consisting of 16
17
4. Process according to claim 1 , wherein the carotenoid compound is
5. Process according to any of the preceding claims wherein the are alkali hydroxide and/or earth alkali hydroxide are those of formulae Mn+(OH)n,
wherein
M is an alkali or earth alkali metal.
6. Process according to any of the preceding claims, wherein at least one alkali hydroxide is used. 7. Process according to any of claims 1 to 4, wherein NaOH and/or KOH is used, preferably KOH.
8. Process according to any of the preceding claim wherein 0.0001 wt-% to 1 wt.%, based on the total weight of the compound(s) of formula (I), of the at least one alkali hydroxide and/or earth alkali hydroxide is used.
9. A formulation comprising at least one carotenoid compound of formula (I)
wherein Ri and R2 are independently of each other
and 0.0001 to 1 wt-%, based on the total weight of the compound(s) of formula (I), of the at least one alkali hydroxide and/or earth alkali hydroxide.
10. Formulation according to claim 9 wherein the carotenoid compounds are chosen from the group consisting of
20
2. Formulation according to claim 9, wherein the carotenoid compound is
13. Formulation according to any of the preceding claims 9 to 12 wherein the alkali hydroxides are used.
14. Formulation according to any of the preceding claims 9 to 13, wherein the alkali hydroxides are NaOH or KOH. 15. Formulation according to any of claims 9 to 13, wherein KOH is used.
16. Formulation according to any of the preceding claims comprising 0.0001 wt-% to 0.8 wt-%, based on the total weight of the compound(s) of formula (I), of at least one alkali hydroxide and/or earth alkali hydroxide.
17. Use of at least one formulation according to any of the preceding claims 9 to 16 in food, feed or personal care products.
18. Food, feed or personal care product comprising at least one formulation of claims 9 to 16.
EP17700460.3A 2016-01-18 2017-01-17 Process for the maintaining of a ratio of isomers of carotenoids Withdrawn EP3405167A1 (en)

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PCT/EP2017/050869 WO2017125379A1 (en) 2016-01-18 2017-01-17 Process for the maintaining of a ratio of isomers of carotenoids

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US20150011648A1 (en) 2011-07-15 2015-01-08 Dsm Ip Assets B.V. Process for the maintaining of a ratio of isomers of carotenoid compounds
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